EP0043303A1 - Verfahren zur Isomerisierung und/oder Umlagerung von Polychlorbenzolen - Google Patents
Verfahren zur Isomerisierung und/oder Umlagerung von Polychlorbenzolen Download PDFInfo
- Publication number
- EP0043303A1 EP0043303A1 EP81400952A EP81400952A EP0043303A1 EP 0043303 A1 EP0043303 A1 EP 0043303A1 EP 81400952 A EP81400952 A EP 81400952A EP 81400952 A EP81400952 A EP 81400952A EP 0043303 A1 EP0043303 A1 EP 0043303A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- chr
- benzene
- formula
- carbon atoms
- trichloro
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 43
- 230000008569 process Effects 0.000 title claims abstract description 17
- 238000006317 isomerization reaction Methods 0.000 title claims abstract description 9
- 230000008707 rearrangement Effects 0.000 title claims abstract description 9
- GBDZXPJXOMHESU-UHFFFAOYSA-N 1,2,3,4-tetrachlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1Cl GBDZXPJXOMHESU-UHFFFAOYSA-N 0.000 claims abstract description 23
- CEOCDNVZRAIOQZ-UHFFFAOYSA-N pentachlorobenzene Chemical compound ClC1=CC(Cl)=C(Cl)C(Cl)=C1Cl CEOCDNVZRAIOQZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 18
- 150000001875 compounds Chemical class 0.000 claims abstract description 18
- 150000001408 amides Chemical class 0.000 claims abstract description 17
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003352 sequestering agent Substances 0.000 claims abstract description 14
- 230000000536 complexating effect Effects 0.000 claims abstract description 12
- CKAPSXZOOQJIBF-UHFFFAOYSA-N hexachlorobenzene Chemical compound ClC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl CKAPSXZOOQJIBF-UHFFFAOYSA-N 0.000 claims abstract description 12
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 8
- 125000004429 atom Chemical group 0.000 claims abstract description 7
- 150000001768 cations Chemical class 0.000 claims abstract description 7
- 239000003513 alkali Substances 0.000 claims abstract description 6
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229920000570 polyether Polymers 0.000 claims abstract description 5
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 4
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical compound [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 claims abstract description 3
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- 229940117389 dichlorobenzene Drugs 0.000 claims abstract description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 78
- 239000000203 mixture Substances 0.000 claims description 35
- 150000001412 amines Chemical class 0.000 claims description 31
- 239000007983 Tris buffer Substances 0.000 claims description 29
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- -1 alkyl radical Chemical class 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 19
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 19
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- XGLVDUUYFKXKPL-UHFFFAOYSA-N 2-(2-methoxyethoxy)-n,n-bis[2-(2-methoxyethoxy)ethyl]ethanamine Chemical compound COCCOCCN(CCOCCOC)CCOCCOC XGLVDUUYFKXKPL-UHFFFAOYSA-N 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 5
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 150000003254 radicals Chemical class 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- 239000003849 aromatic solvent Substances 0.000 claims description 2
- WCYWZMWISLQXQU-UHFFFAOYSA-N methyl Chemical compound [CH3] WCYWZMWISLQXQU-UHFFFAOYSA-N 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 229910052744 lithium Inorganic materials 0.000 claims 1
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- ODZPKZBBUMBTMG-UHFFFAOYSA-N sodium amide Chemical compound [NH2-].[Na+] ODZPKZBBUMBTMG-UHFFFAOYSA-N 0.000 description 13
- XKEFYDZQGKAQCN-UHFFFAOYSA-N 1,3,5-trichlorobenzene Chemical compound ClC1=CC(Cl)=CC(Cl)=C1 XKEFYDZQGKAQCN-UHFFFAOYSA-N 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 0 *c(c(N)c1)c(*)c(N)c1N Chemical compound *c(c(N)c1)c(*)c(N)c1N 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- JHBKHLUZVFWLAG-UHFFFAOYSA-N 1,2,4,5-tetrachlorobenzene Chemical compound ClC1=CC(Cl)=C(Cl)C=C1Cl JHBKHLUZVFWLAG-UHFFFAOYSA-N 0.000 description 4
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 150000003983 crown ethers Chemical class 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 238000003760 magnetic stirring Methods 0.000 description 3
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 101000650578 Salmonella phage P22 Regulatory protein C3 Proteins 0.000 description 2
- 101001040920 Triticum aestivum Alpha-amylase inhibitor 0.28 Proteins 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 125000001196 nonadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- QZYNWJQFTJXIRN-UHFFFAOYSA-N 1,2,3,5-tetrachlorobenzene Chemical compound ClC1=CC(Cl)=C(Cl)C(Cl)=C1 QZYNWJQFTJXIRN-UHFFFAOYSA-N 0.000 description 1
- FWAJPSIPOULHHH-UHFFFAOYSA-N 1,2,4-tribromobenzene Chemical compound BrC1=CC=C(Br)C(Br)=C1 FWAJPSIPOULHHH-UHFFFAOYSA-N 0.000 description 1
- YWDUZLFWHVQCHY-UHFFFAOYSA-N 1,3,5-tribromobenzene Chemical compound BrC1=CC(Br)=CC(Br)=C1 YWDUZLFWHVQCHY-UHFFFAOYSA-N 0.000 description 1
- ZPQOPVIELGIULI-UHFFFAOYSA-N 1,3-dichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1 ZPQOPVIELGIULI-UHFFFAOYSA-N 0.000 description 1
- ISHYFWKKWKXXPL-UHFFFAOYSA-N 1-bromo-2,4-dichlorobenzene Chemical compound ClC1=CC=C(Br)C(Cl)=C1 ISHYFWKKWKXXPL-UHFFFAOYSA-N 0.000 description 1
- DZHFFMWJXJBBRG-UHFFFAOYSA-N 1-bromo-3,5-dichlorobenzene Chemical compound ClC1=CC(Cl)=CC(Br)=C1 DZHFFMWJXJBBRG-UHFFFAOYSA-N 0.000 description 1
- ROJJKFAXAOCLKK-UHFFFAOYSA-N 1-bromo-4-chloro-2-iodobenzene Chemical compound ClC1=CC=C(Br)C(I)=C1 ROJJKFAXAOCLKK-UHFFFAOYSA-N 0.000 description 1
- GVWUUPHBAZERQS-UHFFFAOYSA-N 2,4-dibromo-1-iodobenzene Chemical compound BrC1=CC=C(I)C(Br)=C1 GVWUUPHBAZERQS-UHFFFAOYSA-N 0.000 description 1
- GCRPYRGGTDLAOS-UHFFFAOYSA-N 2-[bis(1-hydroxypropan-2-yl)amino]propan-1-ol Chemical compound OCC(C)N(C(C)CO)C(C)CO GCRPYRGGTDLAOS-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- BOQCLTONMKTZBK-UHFFFAOYSA-N C1OCCOc2ccccc2[U]CCOCCOc(cccc2)c2OC1 Chemical compound C1OCCOc2ccccc2[U]CCOCCOc(cccc2)c2OC1 BOQCLTONMKTZBK-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 229910021055 KNH2 Inorganic materials 0.000 description 1
- UDQAFYPBHTVESC-UHFFFAOYSA-N NC(C(N)=C(C1)I)=CC1=N Chemical compound NC(C(N)=C(C1)I)=CC1=N UDQAFYPBHTVESC-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 125000002619 bicyclic group Chemical group 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 150000004816 dichlorobenzenes Chemical class 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001640 fractional crystallisation Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/35—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction
- C07C17/358—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction by isomerisation
Definitions
- the present invention relates to a process for isomerization and / or rearrangement of polychlorobenzenes. It relates more particularly to a process for the preparation of polychlorobenzenes by rearrangement and / or isomerization of polychlorobenzenes.
- this publication describes the obtaining, from 1-iodo-2,4-dibromo-benzene, of the mixture containing the 1,3,5 isomer as well as the 1,2,4-tribromo benzene, the tribromo -1.3.5 benzene and bromo-1 diodo-3.5 benzene.
- This same publication also describes the reaction of NaNH 2 in liquid ammonia with 1-bromo-2,4-dichloro-benzene, iodo-1-bromo-4 chlorobenzene and iodo-1-tribromo-2,4,6 benzene.
- the method according to the invention achieves this objective and therefore performs a reaction which has never been possible in the prior art.
- the compound complexing the cation of the alkaline amide and / or the alcoholate is a sequestering agent of formula: N- [CHR 1 -CHR 2 O- (CHR 3 -CHR 4 -O) n R 5 ] 3 (I) in which is not an integer greater than or equal to 0 and less than or equal to about 10 (0 ⁇ n ⁇ 10), R I, R 2, R 3 and R 4 e n-id or different represent a hydrogen atom or an alkyl radical having from 1 to 4 carbon atoms and R 5 represents an alkyl or cycloalkyl radical having from 1 to 12 carbon atoms, a phenyl radical or a radical -C m H 2 m- ⁇ or C m H 2m + 1 - ⁇ -, where m is between 1 and 12 (1 ⁇ m ⁇ 12).
- the complexing compound is a macrocyclic polyether having 15 to 30 atoms in the ring and consisting of 4 to 10 -OX units in which X is either -CHR 6 -CHR 7 - either -CHR 6 -CHR 8 -CR 9R 7 - 'R 6 , R 7 , R 8 and R 9 identical or different being a hydrogen atom or an alkyl radical having from 1 to 4 carbon atoms, one of X may be -CHR 6 -CHR 8 -CR 9 R 7 - when the units -0-X include the group -O-CHR 6 -CHR 7 -.
- a mixture of at least two of the complexing compounds defined above is used.
- the dichlorobenzenes used in the process according to the invention are 1,2-dichloro-benzene, 1,3-dichloro-benzene and 1,4-dichloro-benzene.
- the trichlorobenzenes concerned are 1,2,3,3-trichloro benzene, 1,2,4,4-trichlorobenzene, and 1,3,5-trichlorobenzene.
- tetrachlorobenzenes are tetrachloro-1,2,4,5 benzene, tetrachloro-1,2,3,5 benzene and tetrachloro-1,2,3,4 benzene.
- the invention is based on the fact that a complexing compound forms with the alkaline amide and / or the alkali alcoholate a complex which allows the extraction of a hydrogen from a polychlorobenzene which give a carbanion.
- This carbanion due to the complexation of the alkaline cation is soluble in the medium which allows it to extract chlorine from another polychlorobenzene molecule, the reaction reproducing according to the same scheme with the other species present in the reaction medium. .
- the amide or alcoholate anion extracts a hydrogen from the trichlorobtinzene to give the following three carbantons: in variable proportions depending on the acidity of the hydrogen torn off. It is the CI carbanion which will be the majority here, but it will be the CIII carbanion which will be the most reactive in the following stage of pulling out a chlorine atom from the pentachlorobenzene.
- carbanion CIII on pentachlorobenzene. mainly gives the carbanion: resulting from the tearing of chlorine 3 from pentachlorobenzene (other carbanions are formed by tearing of a chlorine atom on the other sites, but in smaller proportions) and tetrachloro-1,2,3,5:
- 1,2,4,4-trichloro benzene can be transformed into 1,3,5-trichloro benzene.
- a tetrachlorobenzene such as' tetrachloro-1,2,4,5 benzene
- trichloro-1,2,4 benzene under the conditions of the invention, this disappearance is observed. the latter in favor of 1,3,5-trichlorobenzene.
- a sequestering agent of formula (I) is used in which R 1 , R 2 , R 3 and R 4 represent a hydrogen atom or a methyl radical, R 5 and n having the previous meaning.
- n is greater than or equal to 0 and less than uu equal to 6 and for which R 5 represents an alkyl radical having from 1 to 4 carbon atoms.
- the macrocyclic polyethers which can be used in the process according to the invention are known by the general name of "crown ethers" and are described in French patent 69.43879 published under number 2,026,481.
- crown ethers which can be used according to the invention are:
- the process according to the invention can be carried out in the presence or in the absence of solvent.
- it is the starting polychlorobenzene (s) which plays the role of solvent.
- the latter must meet a certain number of conditions: it must first of all dissolve the sequestering agent (the latter is soluble in most of the usual solvents) and the polychlorobenzenes; it must also be chemically inert with respect to polychlorobenzenes and amide.
- An aromatic solvent is preferably chosen, such as, for example, chlorobenzene, benzene or toluene.
- the choice of the sequestering agent most suited to the implementation of the method according to the invention is also made, taking into account the size of the alkali metal cation of the amide.
- alkali metal amide (s) used in the context of the process according to the invention are chosen from the group comprising NaNH 2 , KNH2 , L i NH2 . We prefer to use NaNH 2 .
- the alkali alcoholate (s) used in the context of the process according to the invention are chosen from the group comprising the compounds R0 - M + where M + preferably represents Na + and K + and where R represents an alkyl radical preferably containing 1 to 6 carbon atoms. Mention may be made, as an example, of sodium and potassium t-butylates.
- the method according to the invention is preferably carried out at a temperature between -20 ° C and 60 ° C. Even more preferably, the reaction takes place between 0 and 40 ° C.
- the sequestering agent is used in an amount such that the molar ratio of the sequestering agent of formula (I) to the alkaline amide is preferably between approximately 0.005 and approximately 0.5. Even more preferably, this ratio is between approximately 0.02 and approximately 0.2.
- the molar ratio of the alkali amide to the starting polychlorobenzene (s) is preferably between approximately 1 and approximately 0.05. Even more preferably, it is between approximately 0.5 and approximately 0.05.
- the proportions of the starting polychlorohenzenes, when a mixture of these is used, can vary within wide limits. These proportions are not a critical element of the invention.
- 1,3,5-trichloro benzene is an intermediate of great importance for the synthesis of compounds with phytosanitary activity which is obtained in the prior art according to delicate and costly implementation methods such as for example, by chlorination of 1-bromo-3,5-dichloro benzene, in the presence of an azobisnitrile compound or a benzoyl peroxide (Japanese patent application 78.18797).
- the invention therefore also relates to an isomerization and / or rearrangement process as defined above, for the preparation of 1,3,5-trichloro benzene characterized in that the reaction is carried out, at least a tetrachlorobenzene optionally mixed with 1,2,3,3-trichlorobenzene and / or 1,2,4-trichlorobenzene and / or pentachlorobenzene and / or hexachlorobenzene.
- a mixture of têtrachloro-1,2,4,5 benzene and trichloro-1,2,4 benzene is used.
- 1,2,4,5-tetrachloro benzene and 1,2,4-trichloro benzene are used in amounts such that the molar ratio of tetrachloro to trichloro is between approximately 0.1 and approximately 10.
- the polychlorobenzene mixture obtained at the end of the reaction is separated according to techniques well known to those skilled in the art, for example by distillation and / or fractional crystallization.
- the sequestering agents of formula (I) used in the process according to the invention can be prepared as described in the French patent application published under the number 2.450.120.
- tetrachlorobenzene 1 2 4 5 or 21.8 g 0.1 mol of tetrachlorobenzene 1 2 4 5 or 21.8 g is then introduced under nitrogen (anhydrous) into a 250 ml reactor equipped with a condenser and a magnetic stirrer, followed by making up to 100 g with anhydrous chlorobenzene .
- the mixture is stirred and cooled to 15 ° C.
- 0.005 mole of tris (3.6-dioxa heptyl) amine is then added, ie 1.6 g and 3.9 g of a mixture of sodium amide in toluene (50% - 50%), or approximately 0.05 mole of sodium amide.
- Example No. 1 Under the operating conditions used in Example No. 1, 0.1 mol of tetrachlorobtenzene-1,2,3,4, or 21.8 g, is introduced under nitrogen, then it is made up to 100 g with anhydrous chlorobenzene. 0.005 mole of tris (dioxa-3.6 heptyl) amine is added, ie 1.6 g and 2 g of sodium amide in solution in toluene. An increase in temperature is observed from 19 ° C to 25 ° C. After 2 h of reaction, with stirring, the composition of the polychlorobenzenes is as follows:
- the mixture is stirred at room temperature of 18 ° C.
- crown ether "Dicyclohexyl 18 C-6" of formula: or 0.93 g and a me Lange of sodium amide in toluene (50% - 50%) or about 0.02 mole of sodium amide.
- the mixture is stirred at room temperature of 19 ° C.
- a temperature of 17 ° C is maintained for 2 hours.
- reaction mixture is then taken up in 200 ml of water and 50 ml of dichloromethane.
- organic layer is then analyzed:
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT81400952T ATE4699T1 (de) | 1980-07-01 | 1981-06-16 | Verfahren zur isomerisierung und/oder umlagerung von polychlorbenzolen. |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8014607A FR2486068A1 (fr) | 1980-07-01 | 1980-07-01 | Procede d'isomerisation et/ou de rearrangement de polychlorobenzenes |
| FR8014607 | 1980-07-01 | ||
| FR8109392A FR2505817A1 (fr) | 1981-05-12 | 1981-05-12 | Procede d'isomerisation et/ou de rearrangement de polychlorobenzenes |
| FR8109392 | 1981-05-12 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0043303A1 true EP0043303A1 (de) | 1982-01-06 |
| EP0043303B1 EP0043303B1 (de) | 1983-09-21 |
Family
ID=26221868
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP81400952A Expired EP0043303B1 (de) | 1980-07-01 | 1981-06-16 | Verfahren zur Isomerisierung und/oder Umlagerung von Polychlorbenzolen |
Country Status (3)
| Country | Link |
|---|---|
| US (1) | US4629815A (de) |
| EP (1) | EP0043303B1 (de) |
| DE (1) | DE3160950D1 (de) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4479022A (en) * | 1981-04-08 | 1984-10-23 | Rhone-Poulenc Specialites Chimiques | Isomerization of bromohalogenobenzenes |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8716587D0 (en) * | 1987-07-14 | 1987-08-19 | Shell Int Research | Preparing thiophene derivatives |
| US5030777A (en) * | 1989-10-31 | 1991-07-09 | Standard Chlorine Of Delaware, Inc. | Synthesis of 3,5-dichloroalkylbenzene and recovery of 1,3-dichlorobenzene |
| JPH04112843A (ja) * | 1990-09-03 | 1992-04-14 | Toray Ind Inc | トリクロルベンゼンの異性化方法 |
| US5235020A (en) * | 1991-12-31 | 1993-08-10 | Amoco Corporation | Process for preparation of poly(aryl ether) polymers by acyclic catalysts |
| CN101891587B (zh) * | 2010-07-19 | 2012-05-23 | 扬州大学 | 间三氯苯的制备方法 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1061506A (fr) * | 1951-10-04 | 1954-04-13 | Union Carbide & Carbon Corp | Isomérisation des dichlorobenzènes |
| US2866829A (en) * | 1956-03-26 | 1958-12-30 | Woodruff Douglas | Isomerization of polychlorobenzenes |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2355337A (en) * | 1942-08-28 | 1944-08-08 | Rohm & Haas | Preparation of ether amines |
| FR2459216A1 (fr) * | 1979-06-20 | 1981-01-09 | Rhone Poulenc Ind | Procede de preparation d'ethers aryliques |
-
1981
- 1981-06-16 DE DE8181400952T patent/DE3160950D1/de not_active Expired
- 1981-06-16 EP EP81400952A patent/EP0043303B1/de not_active Expired
- 1981-06-23 US US06/276,481 patent/US4629815A/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1061506A (fr) * | 1951-10-04 | 1954-04-13 | Union Carbide & Carbon Corp | Isomérisation des dichlorobenzènes |
| US2866829A (en) * | 1956-03-26 | 1958-12-30 | Woodruff Douglas | Isomerization of polychlorobenzenes |
Non-Patent Citations (1)
| Title |
|---|
| Journal of the American Chemical Society, Vol. 93, 10 Mars 1971, Easton (US) J.F. BUNNETT et al.: "Isomerization and Disproportionation of Trihalobenzenes Catalyzed by Potassium Analide in Liquid Ammonia", pages 1183-1190 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4479022A (en) * | 1981-04-08 | 1984-10-23 | Rhone-Poulenc Specialites Chimiques | Isomerization of bromohalogenobenzenes |
Also Published As
| Publication number | Publication date |
|---|---|
| DE3160950D1 (en) | 1983-10-27 |
| EP0043303B1 (de) | 1983-09-21 |
| US4629815A (en) | 1986-12-16 |
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